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Aryl-bridged 1-hydroxypyridin-2-one: sensitizer ligands for Eu(III).

ABSTRACT: The synthesis, crystal structure, solution stability, and photophysical properties of an aryl group bridging two 1-hydroxypyridin-2-one units complexed to Eu(III) are reported. The results show that this backbone unit increases the rigidity of the ensuing complex, and also the conjugation of the ligand. As a result of the latter, the singlet absorption energy is decreased, along with the energy of the lowest excited triplet state. The resulting efficiency of sensitization for the Eu(III) ion is influenced by these phenomena, yielding an overall quantum yield of 6.2% in aqueous solution. The kinetic parameters arising from the luminescence data reveal an enhanced nonradiative decay rate for this compound when compared to previously reported aliphatic bridges.

SUBMITTER: D'Aleo A

PROVIDER: S-EPMC3176675 | biostudies-literature | 2008 Jul

REPOSITORIES: biostudies-literature

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Aryl-bridged 1-hydroxypyridin-2-one: sensitizer ligands for Eu(III).

D'Aléo Anthony A Xu Jide J Moore Evan G EG Jocher Christoph J CJ Raymond Kenneth N KN

Inorganic chemistry 20080614 14

The synthesis, crystal structure, solution stability, and photophysical properties of an aryl group bridging two 1-hydroxypyridin-2-one units complexed to Eu(III) are reported. The results show that this backbone unit increases the rigidity of the ensuing complex, and also the conjugation of the ligand. As a result of the latter, the singlet absorption energy is decreased, along with the energy of the lowest excited triplet state. The resulting efficiency of sensitization for the Eu(III) ion is ...[more]

PMID: 18553909

Similar Datasets

Aryl bridged 1-hydroxypyridin-2-one: effect of the bridge on the Eu(III) sensitization process.

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| S-EPMC3174140 | biostudies-literature

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2019-10-01 | GSE121101 | GEO

Electronic Structures and Reactivity Profiles of Aryl Nitrenoid-Bridged Dicopper Complexes.

Project description:Dicopper complexes templated by dinucleating, pacman dipyrrin ligand scaffolds (Mesdmx, tBudmx: dimethylxanthine-bridged, cofacial bis-dipyrrin) were synthesized by deprotonation/metalation with mesitylcopper (CuMes; Mes: mesityl) or by transmetalation with cuprous precursors from the corresponding deprotonated ligand. Neutral imide complexes (Rdmx)Cu2(?2-NAr) (R: Mes, tBu; Ar: 4-MeOC6H4, 3,5-(F3C)2C6H3) were synthesized by treatment of the corresponding dicuprous complexes with aryl azides. While one-electron reduction of (Mesdmx)Cu2(?2-N(C6H4OMe)) with potassium graphite initiates an intramolecular, benzylic C-H amination at room temperature, chemical reduction of (tBudmx)Cu2(?2-NAr) leads to isolable [(tBudmx)Cu2(?2-NAr)]- product salts. The electronic structures of the thermally robust [(tBudmx)Cu2(?2-NAr)]0/- complexes were assessed by variable-temperature electron paramagnetic resonance spectroscopy, X-ray absorption spectroscopy (Cu L2,3/K-edge, N K-edge), optical spectroscopy, and DFT/CASSCF calculations. These data indicate that the formally Class IIIA mixed valence complexes of the type [(Rdmx)Cu2(?2-NAr)]- feature significant NAr-localized spin following reduction from electronic population of the [Cu2(?2-NAr)] ?* manifold, contrasting previous methods for engendering iminyl character through chemical oxidation. The reactivity of the isolable imido and iminyl complexes are examined for prototypical radical-promoted reactivity (e.g., nitrene transfer and H-atom abstraction), where the divergent reactivity is rationalized by the relative degree of N-radical character afforded from different aryl substituents.

| S-EPMC7262786 | biostudies-literature

Acetate-bridged platinum(III) complexes derived from cisplatin.

Project description:Oxidation of the acetate-bridged half-lantern platinum(II) complex cis-[Pt(II)(NH(3))(2)(μ-OAc)(2)Pt(II)(NH(3))(2)](NO(3))(2), [1](NO(3))(2), with iodobenzene dichloride or bromine generates the halide-capped platinum(III) species cis-[XPt(III)(NH(3))(2)(μ-OAc)(2)Pt(III)(NH(3))(2)X](NO(3))(2), where X is Cl in [2](NO(3))(2) or Br in [3](NO(3))(2), respectively. These three complexes, characterized structurally by X-ray crystallography, feature short (≈2.6 Å) Pt-Pt separations, consistent with formation of a formal metal-metal bond upon oxidation. Elongated axial Pt-X distances occur, reflecting the strong trans influence of the metal-metal bond. The three structures are compared to those of other known dinuclear platinum complexes. A combination of (1)H, (13)C, (14)N, and (195)Pt NMR spectroscopy was used to characterize [1](2+)-[3](2+) in solution. All resonances shift downfield upon oxidation of [1](2+) to [2](2+) and [3](2+). For the platinum(III) complexes, the (14)N and (195)Pt resonances exhibit decreased line widths by comparison to those of [1](2+). Density functional theory calculations suggest that the decrease in the (14)N line width arises from a diminished electric field gradient at the (14)N nuclei in the higher valent compounds. The oxidation of [1](NO(3))(2) with the alternative oxidizing agent bis(trifluoroacetoxy)iodobenzene affords the novel tetranuclear complex cis-[(O(2)CCF(3))Pt(III)(NH(3))(2)(μ-OAc)(2)Pt(III)(NH(3))(μ-NH(2))](2)(NO(3))(4), [4](NO(3))(4), also characterized structurally by X-ray crystallography. In solution, this complex exists as a mixture of species, the identities of which are proposed.

| S-EPMC3457664 | biostudies-literature

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